DE10006823C2 - Process for producing a flexible metallic substrate for a CIS solar cell and CIS solar cell - Google Patents
Process for producing a flexible metallic substrate for a CIS solar cell and CIS solar cellInfo
- Publication number
- DE10006823C2 DE10006823C2 DE10006823A DE10006823A DE10006823C2 DE 10006823 C2 DE10006823 C2 DE 10006823C2 DE 10006823 A DE10006823 A DE 10006823A DE 10006823 A DE10006823 A DE 10006823A DE 10006823 C2 DE10006823 C2 DE 10006823C2
- Authority
- DE
- Germany
- Prior art keywords
- nickel
- layer
- cis
- solar cell
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000758 substrate Substances 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 14
- 230000009975 flexible effect Effects 0.000 title claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 239000011889 copper foil Substances 0.000 claims description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 9
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 9
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims 1
- 239000010410 layer Substances 0.000 description 67
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 230000004888 barrier function Effects 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000012876 carrier material Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001374 Invar Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 101150049168 Nisch gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
- H01L31/03928—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines flexiblen metallischen Substrats für eine CIS-Solarzelle und eine nach diesem Verfahren hergestellte CIS-Solarzelle.The invention relates to a method for producing a flexible metallic substrate for a CIS solar cell and a CIS solar cell manufactured using this method.
In dem Bemühen, Strom aus Sonnenlicht ohne Umweltbelastung und zu erzeugen mit Kosten, die in der selben Größenordnung wie die Erzeugungskosten bei der Nutzung fossiler Energieträger liegen, werden große Anstrengungen zur Entwicklung kostengünstiger Solarzellen gemacht. Dabei stellen Dünnschichtsolarmodule den jüngsten Entwicklungsstand dar. Hierbei werden Schichten aus hochreinem Silizium, Kadmium- Tellurid oder Kupfer-Indium-Selenid/Schwefel (abgekürzt CIS) von weniger als 1 µm Dicke, üblicherweise mit Hilfe von Vakuumtechniken, auf Glas aufgedampft.In an effort to generate electricity from sunlight without pollution and to generate with costs of the same order as the generation costs of using fossil fuels great efforts to develop made cheaper solar cells. Put it there Thin-film solar modules represent the latest development. Here layers of high-purity silicon, cadmium Telluride or copper indium selenide / sulfur (CIS for short) of less than 1 µm in thickness, usually with the help of Vacuum techniques, evaporated on glass.
Unter den drei genannten Dünnschicht-Technologien ist die CIS- Technologie wegen ihrer Umweltverträglichkeit und dem Fehlen von Degradation (nachlassende Wirksamkeit durch Altern) besonders interessant. Die CIS-Schicht wird üblicherweise auf Glas, das zumeist erst im Sputterverfahren mit Molybdän beschichtet wurde, abgeschieden.Among the three thin-film technologies mentioned, the CIS Technology because of its environmental compatibility and lack of degradation (decreasing effectiveness through aging) especially interesting. The CIS layer is usually based on Glass, usually only sputtered with molybdenum was coated.
Es sind wegen der Nachteile von Glas als Substrat jedoch verschiedene Anstrengungen unternommen worden, um auch flexible Materialien einsetzen zu können. It is because of the disadvantages of glass as a substrate various efforts have been made to also to be able to use flexible materials.
In der Überlegung, daß die Verwendung von Kupfer als Träger material das elektrochemische Abscheiden der CIS-Schicht er lauben würde und Kupfer selbst Bestandteil der CIS-Schicht ist, wurde mit der DE-A 196 34 580 vorgeschlagen, ein Kup ferband als Trägermaterial zu verwenden. Zunächst wird auf dem Kupferband Indium elektrochemisch abgeschieden. In einem zweiten Schritt wird das Band aufgeheizt und auf die aufge heizte Indium-Schicht in der Dampfphase vorliegendes Selen oder Schwefel aufgebracht, wobei Kupfer in die Indiumschicht eindiffundieren und dort zusammen mit dem Selen/Schwefel die CIS-Schicht bilden soll. Das Verfahren erfordert eine genaue Einhaltung des Temperaturbereiches und der Prozeßzeiten bei der Selenisierung bzw. Sulfidisierung. Außerdem bildet sich an der Oberfläche Kupferselenid bzw. Kupfersulfid, das die Reinheit der CIS-Schicht stören würde und deshalb ätztech nisch wieder entfernt werden muß. Schließlich kann nicht ausgeschlossen werden, daß im Verlauf der Zeit weiteres Kup fer in die CIS-Schicht eindiffundiert und die für den photo voltaischen Effekt nötige Zusammensetzung ändert und somit die Funktion der Solarzelle zunehmend vermindert. Aufgrund der Nutzung der Kupferunterlage für den gleichzeitigen Auf bau der CIS-Schicht ist hier keine Diffusionssperre vorhan den.Considering that the use of copper as a carrier material the electrochemical deposition of the CIS layer would leave and copper itself part of the CIS layer is proposed with DE-A 196 34 580, a Kup tape to use as a backing material. First up electrochemically deposited on the copper tape indium. In one second step, the tape is heated up and onto the heated indium layer selenium present in the vapor phase or sulfur is applied, with copper in the indium layer diffuse in and there together with the selenium / sulfur CIS layer should form. The procedure requires an accurate one Compliance with the temperature range and process times selenization or sulfidization. It also forms on the surface copper selenide or copper sulfide, which the Purity of the CIS layer would interfere and therefore etch-tech niche must be removed again. After all, can't be excluded that further Kup diffused into the CIS layer and used for the photo voltaic effect changes necessary composition and thus the function of the solar cell is increasingly diminished. by virtue of the use of the copper base for simultaneous opening There is no diffusion barrier here to build the CIS layer the.
Ein grundsätzlicher Nachteil von Kupfer ist darüber hinaus, daß der thermische Ausdehnungskoeffizient der kristallinen CIS-Schicht von dem des Kupferbandes derart verschieden ist, daß es bei der Wärmebehandlung, der nach dem Aufbringen der CIS-Schicht erforderlich ist, leicht zur Rißbildung in der CIS-Schicht kommt, womit jede photovoltaische Funktion zu nichte gemacht wird.Another fundamental disadvantage of copper is that the thermal expansion coefficient of the crystalline CIS layer is so different from that of the copper strip that it is in the heat treatment after the application of the CIS layer is required to easily crack in the layer CIS layer comes with what every photovoltaic function is made.
Es wurde auch bereits vorgeschlagen, die CIS-Schicht auf ei ne handelsübliche flexible Molybdänfolie aufzubringen, wie sie beispielsweise für Durchführungen von elektrischen An schlüssen in Halogenlampen verwendet wird. Molybdänfolie hat jedoch den etwa vierfachen Preis von Kupferband. Seine Ver wendung ist, vermutlich wegen der darin enthaltenen Verun reinigungen, nicht über Laborversuche hinausgekommen. It has also been suggested that the CIS layer on egg to apply ne commercially available flexible molybdenum foil, such as they for example for bushings of electrical connections conclusions is used in halogen lamps. Has molybdenum foil however, about four times the price of copper tape. His ver is probably because of the pollution it contains cleaning, did not go beyond laboratory tests.
Ebenfalls bekannt geworden sind Kunststoff-Folien zur CIS- Abscheidung. Die Auswahl genügend hochtemperaturfester Mate rialien bereitet jedoch erhebliche Mühe. Außerdem müssen derartige Folien naturgemäß erst durch ITO/TCO-Schichten e lektrisch leitfähig gemacht werden, was üblicherweise wie derum durch Aufdampfen im Vakuum geschieht, das die Kosten erheblich steigen läßt.Plastic films for CIS have also become known. Deposition. The selection of enough high-temperature resistant mate rialien is, however, very difficult. You also have to such foils naturally only through ITO / TCO layers e be made electrically conductive, which is usually like which is done by vacuum deposition, which is the cost can increase significantly.
Chrom-Nickel-Stahl-Folie, die auch bereits vorgeschlagen wurde, eignet sich ebenfalls wenig, da es dazu neigt, Was serstoff aufzunehmen, das auf der Folienoberfläche Bläschen bildet, die bei der Abscheidung der CIS-Schicht zu "pin ho les" führen, wodurch es beim späteren Aufbringen einer transparenten Deckschicht zu Kurzschlüssen kommt, welche die Solarzelle unbrauchbar machen.Chrome-nickel-steel foil, which has also already been proposed is also unsuitable because it tends to What absorb hydrogen that bubbles on the surface of the film forms, which in the deposition of the CIS layer to "pin ho les ", which makes it easier to apply later transparent cover layer comes to short circuits, which the Make the solar cell unusable.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung eines metallischen Substrates für eine flexible, bandförmige Solarzelle und ein solches Substrat anzugeben, das das galvanische Aufbringen der CIS-Schicht erlaubt und somit keine Vakuumtechnologie erfordert, mit dem das Eindif fundieren von Ionen des Substrats in die CIS-Schicht jedoch verhindert wird. Das Substrat soll unempfindlich sein gegen über mechanischen (Biegen der Zelle) und thermischen Ein flüssen auf die Solarzelle.The invention has for its object a method for Production of a metallic substrate for a flexible, to indicate ribbon-shaped solar cell and such a substrate, that allows the galvanic application of the CIS layer and therefore requires no vacuum technology with which the diff however, base ions of the substrate in the CIS layer is prevented. The substrate is said to be insensitive to about mechanical (bending the cell) and thermal on flow on the solar cell.
Die Aufgabe wird erfindungsgemäß gelöst durch die Merkmale der Ansprüche 1, 2, 3, und 6. Zweckmäßige Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche.The object is achieved by the features of claims 1, 2, 3, and 6. Appropriate configurations the invention are the subject of the dependent claims.
Danach wird als Trägermaterial eine bandförmige Kupferfolie verwendet, auf die galvanisch ein Schichtaufbau aus Nickel oder Nickel-Eisen und Molybdän, Rhodium oder Palladium oder einer Nickel-Palladium-Legierung oder aus Nickel-Eisen und einer Schicht aus einer Nickel-Palladium-Legierung aufge bracht wird.Then a ribbon-shaped copper foil is used as the carrier material used, on the electroplated layer structure made of nickel or nickel iron and molybdenum, rhodium or palladium or a nickel-palladium alloy or nickel-iron and a layer of a nickel-palladium alloy is brought.
Die Beeinflussung der Eigenschaften von Kupferfolien durch eine Beschichtung mit Nickel-Palladium ist an sich bereits bekannt, so aus Abys et al., The Electrodeposition and Mate rial Properties of Palladium-Nickel Alloys, Metal Finishing, July 1991, 43-52 oder Galvanische Abscheidung von Palladi um und Palladiumlegierungen, Galvanotechnik 84 (1993) Nr. 8, 2578-2584. Derartige Substrate dienen aber bisher nur als Kontaktmaterialien oder als Material für Schmuckstücke (Ein sparung von Edelmetallen). Für die Herstellung von CIS- Solarzellen wurden sie nicht erwogen.The influencing of the properties of copper foils by coating with nickel-palladium is already known per se, for example from Abys et al., The Electrodeposition and Material Properties of Palladium-Nickel Alloys, Metal Finishing, July 1991 , 43-52 or galvanic deposition von Palladi um and Palladium alloys, Galvanotechnik 84 ( 1993 ) No. 8, 2578-2584. Such substrates have so far only served as contact materials or as material for jewelry (a saving of precious metals). They were not considered for the manufacture of CIS solar cells.
Die Schicht aus Molybdän, Rhodium oder Palladium übernimmt die "Vermittlung" zwischen den sehr unterschiedlichen ther mischen Ausdehnungskoeffizienten von Kupfer/Nickel und CIS, während Nickel bzw. Nickel-Eisen die Festigkeit des Schich tenverbundes erheblich erhöht und eine Diffusionsbarriere gegenüber Kupferionen darstellt. Molybdän hat einen sehr ge ringen, der CIS-Schicht ähnlichen thermischen Ausdehnungs koeffizienten, andererseits einen hohen Elastizitätsmodul, der die Spannungen zwischen den darunter und darüberliegen den Schichten unterschiedlicher Ausdehnung aufzunehmen ver mag. Schichten aus Rhodium oder Palladium verhalten sich ähnlich, d. h. sie zeigen bei niedriger Wärmeausdehnung eine hohe Elastizität.The layer made of molybdenum, rhodium or palladium takes over the "mediation" between the very different ther mix expansion coefficients of copper / nickel and CIS, while nickel or nickel-iron the strength of the layer tenverbundes significantly increased and a diffusion barrier towards copper ions. Molybdenum has a very wrestle, thermal expansion similar to the CIS layer coefficients, on the other hand a high modulus of elasticity, which are the tensions between those below and above to absorb the layers of different dimensions like. Layers of rhodium or palladium behave similar, d. H. they show one at low thermal expansion high elasticity.
Als Verbundsystem stellt der Schichtenaufbau somit ein ge eignetes Substrat dar, das ausschließlich im bandgalvanoche mischen Verfahren herstellbar ist und das trotz der an sich hohen Kosten von Molybdän, Rhodium und Palladium wegen der geringen Schichtdicken insgesamt preiswert ist.As a composite system, the layer structure is thus a ge suitable substrate that is only in the band galvano mixing process can be produced and that in spite of itself high cost of molybdenum, rhodium and palladium because of the low layer thicknesses is inexpensive overall.
Kupferfolie hat den Vorteil, daß sie flexibel und preiswer ter als andere Metallfolien ist. Die außerdem gute Leitfä higkeit ist nicht von allzu großer Bedeutung, da photovol taisch erzeugter Strom eine geringe Stromdichte besitzt. Es können daher auch Kupferlegierungen, die eine geringere Leitfähigkeit aufweisen, jedoch andere Vorteile besitzen, verwendet werden.Copper foil has the advantage that it is flexible and inexpensive ter than other metal foils. The also good guide ability is not too important since photovol Electrically generated electricity has a low current density. It can therefore also use copper alloys that have a lower Have conductivity but have other advantages, be used.
Vorteilhaft kann z. B. elektrolytisch abgeschiedene Kupfer folie, die bisher traditionell ausschließlich für die Lei terplattenfertigung benutzt wurde und eine Reihe von bisher bei anderen Anwendungen nicht genutzten bzw. dort nicht ge fragten Vorteilen aufweist, verwendet werden. Die Reinheit und die Zusammensetzung kann durch Legierungsbestandteile und Beimengungen im Elektrolysebad gesteuert werden. Auch läßt sich die Oberfläche mit geringer Rauhigkeit herstellen.Advantageously, e.g. B. electrodeposited copper foil, which was traditionally only for lei has been used and a number of previous not used in other applications or not used there advantages in question can be used. The purity and the composition can by alloying components and admixtures in the electrolysis bath can be controlled. Also the surface can be produced with low roughness.
Kupfer hat an sich allerdings für die Verwendung als Träger material die bereits oben angedeuteten gravierenden Nachtei le, die durch die Erfindung jedoch überwunden werden. However, copper has inherently for use as a carrier material the grave night egg already indicated above le, which are overcome by the invention.
Erstens ist die Warmfestigkeit von Kupfer sehr gering, so daß ohne eine weitere Maßnahme mechanische Beanspruchungen während des nachfolgenden Temperprozesses zur Beschädigung der dünnen CIS-Schicht führen können. Zweiten sind Kupferio nen, wie bereits gesagt, äußerst beweglich, so daß diese bei dem Temperprozeß, aber auch bereits bei der Gebrauchstempe ratur der Solarzellen, in unkontrollierter Menge in die CIS- Schicht einwandern würden. Drittens ist der thermische Aus dehnungkoeffizient von Kupfer von dem der kristallinen CIS- Schicht derart verschieden, daß unter Temperatureinfluß mit einer Rißbildung in der dünnen, aufliegenden CIS- Absorberschicht zu rechnen ist, welches wiederum jede photo voltaische Funktion zunichte macht.First, the heat resistance of copper is very low, so that without any further measure mechanical stresses to damage during the subsequent annealing process of the thin CIS layer. The second are Kupferio NEN, as already said, extremely agile, so that this the tempering process, but also at the temperature of use of the solar cells, in an uncontrolled amount into the CIS Would immigrate to the shift. Third is the thermal off elongation coefficient of copper from that of crystalline CIS Layer so different that under the influence of temperature with a crack formation in the thin, overlying CIS Absorber layer is to be expected, which in turn every photo voltaic function annihilates.
Mit dem erfindungsgemäßen Schichtaufbau wird, wie bereits beschrieben, zunächst eine Nickel- oder Nickel-Eisen-Schicht aufgebracht, die als Diffusionsbarriere, als Anpassung hin sichtlich des Ausdehnungskoeffizienten und als Haftschicht für die nachfolgenden Schichten dient. Die Nickel-Eisen- Schicht ist als sogenannte INVAR-Legierung bekannt. Nickel oder Nickel-Eisen kann galvanotechnisch aufgebracht werden. Die nachfolgenden Schichten bestehen aus Molybdän, Palladium oder Rhodium, die sich ebenfalls galvanotechnisch aufbringen lassen.With the layer structure according to the invention, as already described, first a nickel or nickel-iron layer applied that as a diffusion barrier, as an adjustment visible of the coefficient of expansion and as an adhesive layer serves for the subsequent layers. The nickel iron The layer is known as the so-called INVAR alloy. nickel or nickel-iron can be applied by electroplating. The subsequent layers consist of molybdenum, palladium or rhodium, which are also electroplated to let.
Eine weitere Variante ist das alleinige Abscheiden einer Nickel-Palladium-Legierung auf der Kupferfolie, die gleich zeitig als Diffusionsbarriere und als Vermittlungschicht für die CIS-Schicht dient.Another variant is the sole separation of one Nickel-palladium alloy on the copper foil, the same early as a diffusion barrier and as a mediation layer for the CIS layer serves.
Das galvanotechnische Aufbringen einer Molybdänschicht ist bisher wenig bekannt, ist aber möglich.The electroplating is a molybdenum layer Little known so far, but is possible.
Schichten aus Palladium oder Rhodium stellen an sich bereits eine Diffusionsbarriere gegen Kupfer dar, die teuren Edelme talle können jedoch in geringerer Schichtstärke und mit bes serer Haftung sowie ohne die Verunreinigung der Bäder durch Kupfer galvanisch aufgebracht werden, wenn zuvor wenigstens eine dünne Nickelschicht auf die Kupferfolie abgeschieden wird. Layers of palladium or rhodium are already there a diffusion barrier against copper, the expensive Edelme talle can, however, in a lower layer thickness and with bes liability and without contamination of the baths Copper are applied galvanically, if at least beforehand deposited a thin layer of nickel on the copper foil becomes.
Molybdän ist nicht in der Lage, als Diffusionsbarriere für Kupfer zu wirken und benötigt deshalb eine Nickelschicht mit bestimmter Mindestdicke als Unterlage. Andererseits muß der direkte Kontakt der Nickelschicht mit der CIS-Schicht ver mieden werden, weil sich hierbei CIS-Nickel-Komplexe bilden würden, also reines CIS für den kristallinen Aufbau nicht mehr zur Verfügung stünde.Molybdenum is unable to act as a diffusion barrier Copper to work and therefore requires a nickel layer certain minimum thickness as a base. On the other hand, the direct contact of the nickel layer with the CIS layer ver should be avoided because this forms CIS-nickel complexes would not be pure CIS for the crystalline structure more would be available.
Die Kupferfolie soll eine möglichst geringe Oberflächenrau higkeit aufweisen, kann zur Maximierung der späteren Licht aufnahme jedoch oberflächenvergrößert sein, indem während des Herstellungsprozesses, bei galvanisch abgeschiedener Fo lie beim Abscheiden, bereits Auswölbungen eingebracht wer den, ohne daß dabei herstellungstechnisch ein besonderer Mehraufwand entsteht. Solche, z. B. halbkugeligen Auswölbun gen in der Größenordnung von ca. 2 mm lassen sich z. B. leicht durch entsprechende Gestaltung der Abscheidetrommel realisieren. Hierdurch wird bei schräg auf die Solarzelle auftreffender Strahlung die Lichtabsorption und damit die Gesamtleistung erhöht.The copper foil should have the lowest possible surface roughness ability to maximize later light However, the surface can be enlarged by during the manufacturing process, with galvanically separated fo If you leave, bulges have already been introduced the one without being special in terms of manufacturing technology Additional effort arises. Such, e.g. B. hemispherical bulge gene in the order of magnitude of approx. 2 mm can e.g. B. easily by appropriate design of the separation drum realize. This will cause the solar cell to slant incident radiation the light absorption and thus the Overall performance increased.
Auf das Trägermaterial kann die CIS-Schicht dann in bekann ter Weise ebenfalls galvanisch aufgebracht werden, so daß insgesamt ein galvanischer Prozeß vorliegt und keine Vakuu manlagen benötigt werden. Die CIS-Schicht wird anschließend in einem Wärmebhandlungsprozeß aktiviert.The CIS layer can then be applied onto the carrier material ter way are also applied galvanically, so that overall there is a galvanic process and no vacuum systems are needed. The CIS layer is then activated in a heat treatment process.
Die Erfindung soll nachstehend anhand von zwei Ausführungs beispielen noch näher erklärt werden. In den Zeichnungen zeigenThe invention is based on two embodiments examples will be explained in more detail. In the drawings demonstrate
Fig. 1 ein Beispiel für einen Schichtaufbau mit Molybdän auf einem flexiblen Trägermaterial, Fig. 1 is an example of a layer structure of molybdenum on a flexible carrier material,
Fig. 2 ein zweites Beispiel für einen Schichtaufbau mit Palladium/Rhodium und Fig. 2 shows a second example of a layer structure with palladium / rhodium and
Fig. 3 ein drittes Beispiel für einen Schichtaufbau mit einer Nickel-Palladium-Legierung. Fig. 3 shows a third example of a layer structure with a nickel-palladium alloy.
Gemäß Fig. 1 besteht das flexible Substrat aus einer galva nisch abgeschiedenen Kupferfolie 1, auf die galvanochemisch zunächst eine Nickelschicht 3 und dann eine Molybdänschicht 4 aufgebracht wurde. Da Molybdän keine besonders gute Diffu sionssperre für Kupferionen darstellt, muß in diesen Fall eine relativ dicke Nickelschicht, ca. in einer Dicke von 2 µm, aufgebracht werden. Nickel übernimmt dann die Funktion einer Diffusionssperre und erhöht gleichzeitig die Warmfe stigkeit der Kupferfolie 1. Auf die Molybdänschicht 4 kann schließlich in üblicher Weise ebenfalls galvanisch eine CIS- Schicht 5 aufgebracht werden.Referring to FIG. 1, the flexible substrate from a galvanic nisch copper foil 1 on the first galvanochemisch a nickel layer 3, and then a molybdenum layer 4 has been applied. Since molybdenum is not a particularly good diffusion barrier for copper ions, a relatively thick nickel layer, approx. 2 µm thick, must be applied in this case. Nickel then takes over the function of a diffusion barrier and at the same time increases the heat resistance of the copper foil 1 . Finally, a CIS layer 5 can also be galvanically applied to the molybdenum layer 4 in a conventional manner.
Nach dem in Fig. 2 dargestellten Beispiel wird wiederum eine galvanisch abgeschiedene Kupferfolie 1 verwendet, auf die galvanisch zunächst auch eine Nickelschicht 2 abgeschieden wurde, hier allerdings nur mit einer Dicke von ca. 0,2 µm. Erlaubt wird das durch den weiteren Schichtaufbau, nach dem eine Schicht 6 aus Palladium oder Rhodium folgt. Palladium und Rhodium stellen bessere Diffusionsbarrieren dar als Mo lybdän, so daß die Nickelschicht 2 hier allein zur Haftver mittlung benötigt wird. Schließlich folgt wieder die CIS- Schicht in bekannter Weise.According to the example shown in FIG. 2, an electrodeposited copper foil 1 is again used, onto which a nickel layer 2 was first electrodeposited, but here only with a thickness of approximately 0.2 μm. This is permitted by the further layer structure, after which a layer 6 made of palladium or rhodium follows. Palladium and rhodium are better diffusion barriers than Mo lybdenum, so that the nickel layer 2 is needed here only for adhesion mediation. Finally, the CIS layer follows again in a known manner.
In Fig. 3 ist eine dritte Variante gezeigt. Hierbei wurde auf eine Kupferfolie 1 allein eine Nickel(20)-Palladium(80)- Legierungsschicht 7 mittlerer Dicke aufgebracht, wie sie als Standardprodukt in der Bandgalvanik zur Verfügung steht. Auf diese wird dann die CIS-Schicht aufgetragen. A third variant is shown in FIG . In this case, a nickel ( 20 ) -palladium ( 80 ) alloy layer 7 of medium thickness was applied to a copper foil 1 alone, as is available as a standard product in strip electroplating. The CIS layer is then applied to this.
11
Kupferfolie
copper foil
22
Nickelschicht
nickel layer
33
Nickelschicht
nickel layer
44
Molybdänschicht
molybdenum layer
55
CIS-Schicht
CIS-layer
66
Schicht aus Palladium oder Rhodium
Layer of palladium or rhodium
77
Nickel(Nickel(
2020
)-Palladium()-Palladium(
8080
)-Legierungsschicht
) alloy
Claims (6)
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DE10006823A DE10006823C2 (en) | 2000-02-08 | 2000-02-08 | Process for producing a flexible metallic substrate for a CIS solar cell and CIS solar cell |
EP01911618A EP1261990A1 (en) | 2000-02-07 | 2001-02-07 | Flexible metal substrate for cis solar cells, and method for producing the same |
AU2001240599A AU2001240599A1 (en) | 2000-02-07 | 2001-02-07 | Flexible metal substrate for cis solar cells, and method for producing the same |
PCT/EP2001/001313 WO2001057932A1 (en) | 2000-02-07 | 2001-02-07 | Flexible metal substrate for cis solar cells, and method for producing the same |
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WO2012123109A2 (en) | 2011-03-15 | 2012-09-20 | Boraident Gmbh | Method for producing flexible thin film solar cells |
DE102012216026B4 (en) | 2011-09-26 | 2021-12-02 | International Business Machines Corporation | Process for the production of a flexible photovoltaic thin-film cell with an iron diffusion barrier layer and flexible photovoltaic thin-film cell with an iron diffusion barrier layer |
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DE10247856A1 (en) * | 2002-08-16 | 2004-02-26 | Daimlerchrysler Ag | Vehicle body part, useful e.g. as part of roof, boot lid, bonnet, mudguard, door or bumper, has thin film solar cell between support and clear top coat, preferably applied in stages with other layers |
DE102004042306B4 (en) * | 2004-02-17 | 2007-10-04 | Pvflex Solar Gmbh | Method for producing a substrate for flexible thin-film solar cells according to the CIS technology |
US7913381B2 (en) * | 2006-10-26 | 2011-03-29 | Carestream Health, Inc. | Metal substrate having electronic devices formed thereon |
JP4304638B2 (en) | 2007-07-13 | 2009-07-29 | オムロン株式会社 | CIS solar cell and manufacturing method thereof |
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DE19634580A1 (en) * | 1996-08-27 | 1998-03-05 | Inst Solar Technologien | CIS band solar cell - Method and device for their production |
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DE19634580A1 (en) * | 1996-08-27 | 1998-03-05 | Inst Solar Technologien | CIS band solar cell - Method and device for their production |
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Galvanotechnik 84 (1983) Nr.8, S.2578-2584 * |
Metal Finishing, July 1991, S.43-52 * |
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WO2012123109A2 (en) | 2011-03-15 | 2012-09-20 | Boraident Gmbh | Method for producing flexible thin film solar cells |
DE102011014795A1 (en) | 2011-03-15 | 2012-09-20 | Boraident Gmbh | Method for producing flexible thin-film solar cells |
DE102012216026B4 (en) | 2011-09-26 | 2021-12-02 | International Business Machines Corporation | Process for the production of a flexible photovoltaic thin-film cell with an iron diffusion barrier layer and flexible photovoltaic thin-film cell with an iron diffusion barrier layer |
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Inventor name: KALBERLAH, KLAUS, DR., 12587 BERLIN, DE Inventor name: JACOBS, KLAUS, PROF., DR., 12559 BERLIN, DE Inventor name: HOFFMANN, THOMAS, DR., 12555 BERLIN, DE |
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